Resorcinol esters of alpha,alpha-dimethyl aliphatic acids



United States Patent 3,462,468 RESORCINOL ESTERS 0F a,a-DIMETHYLALIPHATIC ACIDS Wallace Edmontlson Taylor and Enrique Roberto Witt,Corpus Christi, Tex., assignors to Celanese Corporation, New York, N.Y.,a corporation of Delaware No Drawing. Continuation-impart of applicationSer. No. 174,378, Feb. 20, 1962. This application Oct. 22, 1964, Ser.No. 405,821

Int. Cl. C07c 69/00, 69/30 U.S. Cl. 260-4105 7 Claims ABSTRACT OF THEDISCLOSURE This invention relates to novel esters of various hydroxyaromatic compounds, e.g. dihydric and trihydric phenols, and variousmonocarboxylic and dicarboxylic acids useful as high temperaturelubricants.

where P is a radical selected from the group consisting of phenylene,diphenylene and diphenylene ether; A and B are each a neoalkyl group; C,D and E are each selected from the group consisting of methyl andphenyl; n is an integer from 4-8; F and G are alkylphenyligroup, withalkyl groups containing 1-9 carbon atoms; and J and K are alkyl groupshaving 8-9 carbon atoms.

It should be understood that this specification will concern itself onlywith the ester functional ,(hydroxy or 3,462,468 Patented Aug. 19, 1969carboxy) cites of the various exemplary compounds set forth herein. Itis of course intended to include in this specification and claims themyriad non-ester functional substituted compounds derived from thosecompounds set forth herein.

It is within the scope of this invention to provide diesters ortriesters of aromatic polyhydroxy compounds where the acid moiety iseither the same or different in each ester linkage. For example, thisinvention includes compounds such as resorcinol dineoheptanoate.Further, where the acid moiety is a dicarboxylic acid and the hydroxylmoiety is polyhydroxy, this invention includes polyesters and it alsoincludes diesters of carboxylic acids which are not polymerized.

More specifically, this invention includes diesters wherein thehydroxyl-containing reactant is a hydroquinone, a catechol, aresorcinol, a bisphenol, a dihydroxynaphthol, or substitution productsthereof such as, for example, 2,5 di-tert-butyl hydroquinone, diphenyldimethyl methane (bisphenol A), 3,4 dihydroxyphenyl ether, and di(4-hydroxy) phenyl ether. This invention even includes such alcohols astrimethylol anisole and esters thereof even though these compounds arenot as thermally stable as other compounds included herein.

Diesters according to this invention suitably use, asthe acid moietyreactant, such acids as pivalic acid, heptanoic acid, dimethylmalonicacid, adipic acid, succinic acid, azelaic acid, sebacic acid,neo-heptanoic acid, neodecanoic acid, neotridecanoic acid, benzoic acid,the acid halide corresponding to these acids, or the anhydride of theseacids where applicable.

It is preferred to utilize a mole ratio of monoacid moieties toalcoholic moieties of at least slightly higher than 1 in order to insurethe full esterification of both phenolic hydroxyl groups. It is furtherpreferred that both phenolic hydroxyl groups be esterified with the sameacid moiety.

This invention also includes esters wherein the hydroxylcontainingreactant is a monohydric compound such as phenol, xylenol, andsubstitution products thereof. More specifically, substituted monohydricarylols according to this invention include compounds corresponding tothe structural formula-- where R is an alkyl radical as for examplep-tert-butyl, m-tert-butyl, p-tert-pentyl, m-tert-pentyl or 1,1,3,3tetra methyl butyl.

Esters according to this invention can sometimes be made by directreaction between the carboxylic acid and hydroxyl moieties set forthabove. Preferably, acid anhydrides are reacted with alcohols to produceappropriate esters and optimumly the hydroxyl moiety is reacted withacid halides, for example, the chloride or bromide, to form the ester.

It is possible to make esters according to this invention by thereactions set forth above without the aid of a catalyst. It ispreferred, however, to utilize a catalyst,

such as dimethylformamide, magnesium chloride or pyridine, for example,in order to increase the efficiency of the esterification reaction andto speed it to completion.

The esterification reaction according to this invention is preferably,though not necessarily, carried out by refluxing a solution of thereactants and the catalyst system in an inert non-olefinic solvent suchas toluene or benzene for example.

The reaction temperature will, of course, depend upon the particularreactants involved but, in general, the reaction temperatures range fromabout to 130 C. It is, of course, desirable to maintain the reaction fora time sufficient to insure the reaction of all the available reactants.Where the reaction involves an acid chloride moiety, the reaction issubstantially complete when hydrogen chloride gas ceases to be evolved.Where the reaction is direct esterification, the cessation of waterevolution signifies that the reaction is substantially complete.

The reaction product is conveniently purified by washing with diluteacid, dilute caustic and neutral water and then striping 01f the solventby flash or vacuum distillation. If necessary or desired, the resultingproduct can be decolorized, e.g., with charcoal, and then filtered.Esterification yields are quite good, often at least about 75% oftheoretical based upon the amount of hydroxyl moiety charged. Yields ashigh as 95% of theoretical are not unsual in the reactions of thisinvention.

The following specific examples serve to further illustrate but notlimit the instant invention.

Example I Resorcinyl dipivalate was prepared by mixing together 79 partsby weight (0.72 mole) of resorcinol, 200 parts by weight of toluenesolvent, and 10 parts by weight of dimethylformamide catalyst. Pivaloylchloride was added to this mixture very slowly, 200 parts by weight(1.65 moles) in thirty minutes, and the reactants were refluxed untilhydrogen chloride ceased to be evolved. After reflux, the reactionproduct was cooled, washed with a 1 N aqueous sodium hydroxide solution,a 1 N hydrochloric acid solution and water; the toluene was removed byvacuum flashing at 100 C. and 1 to 5 mm. Hg absolute; the water wasdecanted; the hot ester product was decolorized with carbon, filtered,and then flashed to evolve 159 parts by weight of product which was awhite crystalline material. The yield was 79% based upon the amount ofresorcinol charged to the reaction.

Example II Resorcinol diheptanoate was prepared by mixing together 165parts by weight (1.5 moles) of resorcinol, 454 parts by weight oftoluene solvent and 23.6 parts by weight of dimethyl formamide catalyst.Heptanoyl chloride was added to this mixture very slowly, 500 parts byweight (3.3 moles) in one hour at 55 to 60 C. and the reactants wererefluxed until hydrogen chloride ceased to be evolved. After reflux thereaction product was cooled, washed 5 times with a 1 N sodium hydroxideaqueous solution, once with 1 N hydrochloric acid solution and twicewith water; the toluene and water were removed by vacuum flashing at 100C. and 1 to 5 mm. Hg absolute; the hot ester product was decolorizedwith carbon, filtered, and then flash-distilled at 205 to 215 C. and 2mm. Hg absolute to evolve 438 parts by weight of product which was acolorless fluid having a boiling point of 205-215 C. at 2 mm. Hgabsolute. The yield was 80% based upon the amount of resorcinol chargedto the reaction.

Example III Hydroquinone diheptanoate was prepared by mixing together165 parts by weight of hydroquinone, 454 parts by weight of toluenesolvent and 23.6 parts by weight of dimethyl formamide catalyst.Heptanoyl chloride was 4 aded to this mixture very slowly, 500 parts byweight (3.3 moles) in 1 hour at 70 C. and the reactants were refluxeduntil hydrogen chloride ceased to be evolved. After reflux, the reactionproduct was cooled, washed with a 1 N sodium hydroxide aqueous solution,a 1 N hydrochloric acid solution and water; the toluene and water wereremoved by vacuum flashing at 100 C. and 1 to 5 mm. Hg absolute; the hotester product was decolorized with carbon, filtered, and thenflash-distilled to evolve 454 parts by weight of crude product which wasthen purified by recrystallization from n-heptane. The yield was 91%based upon the amount of hydroquinone charged.

. Example 1V Bisphenol A (diphenol, dimethyl methane) diheptanoate wasprepared by azeotroping 342 parts by weight (1.5 moles) of bisphenol Awith 440 parts by weight of benzene at 65 to C. until no more water wasremoved. The thus dried mixture was cooled and 14.2 parts by weight ofdimethylformamide was added thereto followed by the slow addition (1hour) of 490 parts by weight (3.3 moles) of heptanoyl chloride. Thereactants were refluxed for 2 hours at 120 C. and the resultant productwas stripped of volatiles by heating to 290 C. at 4 mm. Hg absoluteuntil volatiles ceased to be collected. The residue of the volatilestripping step was washed 5 times with 1 N sodium hydroxide aqueoussolution at 40 to 60 C.; water-washed to neutrality; dehydrated invacuo; decolorized with charcoal; and filtered to evolve 598 parts byweight of product which was a slowly crystallizing yellowish oil. Theyield was based upon the amount of bisphenol A charged.

Example V Resorcinol dineoheptanoate was prepared by mixing 165 parts byweight of resorcinol (1.5 moles), 400 parts by weight of toluene solventand 14.2 parts by weight of dimethylformamide catalyst. Neoheptanoylchloride was slowly added to this mixture, 500 parts by weight (3.4moles) in 2 hours at 70 C. The reactants were heated to C. for 2 hours,cooled to 40 C. and 29.5 parts by weight of pyridine was added thereto.The reaction mixture was then heated to 60 C. for 2 hours, cooled,washed with a l N sodium hydroxide aqueous solution, a 1 N hydrochloricacid solution and water, and vacuum-flashed at 100 C. and 1 to 5 mm. Hgabsolute. The resulting ester was decolorized by heating with charcoal,filtered and then flash-distilled at 157 to 164 C. and 1 mm. Hg absoluteto evolve 205 parts by weight of product. The yield was 41% based uponthe amount of resorcinol charged.

Example VI Bisphenol A (diphenol, dimethyl methane) dineoheptanoate wasprepared by azeotroping 342 parts by weight (1.5 moles) of bisphenol Awith 440 parts by weight of benzene at 65 to 80 C. until no more waterwas removed. The thus dried mixture was cooled and 14.2 parts by weightof dimethyl formamide catalyst was added thereto followed by the slowaddition (1 hour) of 490 parts by weight (3.3 moles) of neoheptanoylchloride. The reactants were refluxed for 1 hour at C. and the resultantproduct was stripped of volatiles by heating to 280 C. at 4 mm. Hgabsolute until no more volatiles were collected. The residue of thevolatile stripping step was washed 5 times with 1 N sodium hydroxideaqueous solution at 40 to 50 C. and waterwashed to neutrality. The oillayer from the water wash was dehydrated in vacuo, decolorized withcharcoal, and filtered to evolve 520 parts by weight of bisphenol Adineoheptanoate product which was a dark yellow oil more viscous thann-heptanoate, which did not tend to crystallize. Theyield was 76.6%based upon the amount of bisphenol A charged.

Example VII Resorcinol dineodecanoate was prepared by mixing 127 partsby weight (1.15 moles) of resorcinol, 400 parts by weight of toluenesolvent, and 14.2 parts by weight of dimethylformamide catalyst. Thissolution was heated to 65 C. and 432 parts by weight (2.27 moles) ofneodecanoyl chloride was slowly added thereto in 1.5 hours. The reactionmixture, which raised in temperature to 75 C. during the acid chlorideaddition, was heated to 90 C. and refluxed, after the acid chlorideaddition was completed, until hydrogen chloride ceased to be evolved.After reflux, the mixture was cooled to 40 C. and 49 parts by weight ofpyridine was added thereto. The mixture was then reheated to 75 C. for30 minutes, cooled, and washed with l N sodium hydroxide aqueoussolution, 1 N hydrochloric acid solution and water. The washed reactionproduct was vacuum-flashed at 100 C. and 1 to 5 mm. Hg absolute,decolorized with charcoal, and vacumm-filtered to evolve 375 parts byweight of product which was a pale orange liquid. The yield was 78%based upon the amount of resorcinol charged.

Example VIII Resorcinol dineotridecanoate was prepared by mixing 137parts by weight (1.25 moles) of resorcinol, 400 parts by weight oftoluene solvent, and 14.2 parts by weight of dimethyl formamidecatalyst. This solution Was heated to 70 C. and 580 parts by weight (2.5moles) of neotridecanoyl chloride was slowly added thereto in 1.5 hours.The reaction mixture was maintained at 70 C. for 2 hours until hydrogenchloride was no longer evolved whereupon the reaction mixture was cooledto 40 C. and 49 parts by weight of pyridine was added thereto. Theresulting mixture was stirred for 1 hour at 40 to 50 C., washed with a 1N hydrochloric acid solution, a 1 N sodium hydroxide solution and thenwater; vacuum flashed at 100 C. and 1 to 5 mm. Hg absolute; decolorizedwith charcoal, and vacuum-filtered to evolve 500 parts by weight ofproduct which was a colorless liquid. The yield was 80% based upon theamount of resorcinol charged.

Example IX Resorcinol benzoate neoheptanoate was prepared by mixing 165parts by weight (1.5 moles) of resorcinol, 300 parts by weight oftoluene solvent, and 4.7 parts by weight of dimethylformamide catalyst.This solution was reacted with 211 parts by weight 1.5 moles) benzoylchloride and 234 parts by weight 1.5 moles) of neoheptanoyl chloride byslowly adding the two chlorides simultaneously to the solution in 2hours at 70 C.

The reaction was maintained at 70 C. for 2 hours until hydrogen chloridewas no longer evolved whereupon the reaction mixture was cooled to 40 C.and 49 parts by weight of pyridine was added thereto. The resultingmixture was stirred for two hours at 60 C., cooled to 40 C., and washedwith 1 N hydrochloric acid, 1 N sodium hydroxide solution and water. Thewashed reaction product was vacuum-flashed at 100 C. and 1 to 5 mm. Hgabsolute to remove the solvent, decolorized with charcoal, andvacuum-filtered to evolve 369 parts by weight of product which was thenflashed to a colorless liquid. The yield was 75% based upon the amountof resorcinol charged. The product was a mixture of esters (resorcinolbenzoate neoheptanoate, resorcinol dibenzoate, and resorcinyldineoheptanoate) Example X Bisphenol A (diphenol, dimethyl methane)dibenzoate was prepared by azeotroping 342 parts by weight 1.5 moles) ofbisphenol A with 908 parts by weight of toluene solvent at 65 to 80 C.until dry, whereupon the solution was cooled to 30 C. and 261 parts byweight (3.3 moles) of pyridine was added thereto. Then 464 parts byweight (3.3 moles) of benzoyl chloride was slowly added whilemaintaining the mixture temperature at 30 to 40 C. to

form a thick slurry, which slurry was heated to C. for 1 hour, cooled to30 C. and then water-washed. The ester product crystallized out in thecooling step and was removed from the running reaction mixture byfiltration. The filtered material was slurried in 1 N hydrochloric acid,filtered, and recrystallized twice from toluene to evolve 445 parts byweight of product which was a colorless crystalline powder. The yieldwas 67% based upon the amount of bisphenol A charged.

Example XI Resorcinol dibenzoate was prepared by mixing 165 grams (1.5moles) of resorcinol, 454 parts by weight of toluene solvent, and 14.2parts by weight of dimethylformamide catalyst. The solution Was heatedto 65 C. and 464 parts by weight (3.3 moles) of benzoyl chloride wasslowly added thereto (over the period of 1 hour). The reactiontemperature was slowly raised to 80 C. and then the reactants wererefluxed for 2 hours at 85 C. until hydrogen chloride ceased to beevolved after which time 1.9 parts by weight of pyridine was added andthe mixture refluxed for an additional 3 hours at C. The reactionproducts were cooled to 30 C., washed with l N sodium hydroxidesolution, 1 N hydrochloric acid and water; vacuum-flashed at 100 C. and1 to 5 mm. Hg absolute to remove solvent until the ester product beganto crystallize out of solution, then reheated to 70 C. to re-dissolvethe ester, decolorized with charcoal, and then cooled to crystallize theproduct which was white crystalline needles. The yield was 85% basedupon the amount of resorcinol charged.

Example XII Hydroquinone dibenzoate was prepared by mixing parts byweight (1.5 moles) of hydroquinane, 454 parts by weight of toluenesolvent, and 20 parts by Weight of dimethylformamide catalyst. Benzoylchloride was slowly added to this solution, 464 parts by weight (3.3moles) in 2 hours, at 70 C. The reaction mixture was refluxed at 100 C.for 2 hours and then cooled to 40 C., 19 parts by weight of pyridine wasadded thereto, and the mixture then refluxed for 3 additional hours. Theester reaction product precipitated directly from the reaction mixtureand was recovered by filtration. Recrystallization of the ester from hotdioxane evolved 310 parts by weight of product which was white. Theyield was 97% based upon the amount of hydroquinone charged.

Example XIII 3,4 dihydroxyphenyl (bisphenol) ether neoheptanoate wasprepared by mixing 76 parts by weight (0.38 mole) of 3,4 dihydroxyphenylether, 2.7 parts by weight of dimethylformamide catalyst and 433 partsby weight of toluene solvent. The mixture was heated to 80 C. and 125parts by weight (0.84 mole) of neoheptanoyl chloride was slowly addedthereto over a period of 30 minutes while the temperature was maintainedbetween 80 C. and 90 C. The reaction was allowed to proceed at thistemperature for 3 hours until evolution of hydrogen chloride gas ceasedwhereupon the reaction mixture was stirred for 1 hour at 90 C. thenwashed with 1 N hydrochloric acid and fresh water. The reaction productwas vacuumflashed at 188 to C. and 0.07 mm. Hg absolute to evolve 137parts by weight of product which was a light yellow mobile oil with aboiling-point range of 188-195 C. at 0.07 mm. Hg absolute. The yield was73% based upon the amount of 3,4 dihydroxyphenyl ether charged.

Example XIV m-(p-Octyl phenoxy) phenyl neoheptanoate was prepared bydissolving =125 parts by weight (0.42 mole) of octyl phenoxy phenol in410 parts by weight of toluene; adding 79 parts by weight of pyridine tothe solution; slowly adding (dropwise) 62 parts by weight (0.42 mole) ofneoheptanoyl chloride; stirring for 1 hour at 30 C.;

7 permitting the mixture to stand overnight; heating for 2 hours at 95C.; and cooling to 30 C. The reaction product was washed with water and1 N hydrochloric acid; stripped of solvent and distilled to give 88parts by weight of product. The yield was 51%.

Example XV p-(p-t-Butylphenoxy)phenyl neoheptanoate was prepared bydissolving 190 parts by weight (0.79 mole) of p(p-t-butylphenoxy) phenoland 2.83 parts by weight of dimethyl formamide catalyst in 600 parts byweight of toluene; slowly adding (dropwise) 129 parts by weight (0.87mole) of neoheptanoyl chloride at 70 to 80 C.; maintaining thistemperature until hydrogen chloride ceased to be evolved; cooling to 30C.; and adding 49 parts by weight of pyridine. The reaction product waspermitted to stand overnight; washed with water; and thenflash-distilled at 166 to 174 C. at 0.3 mm. Hg absolute to give 202parts by weight of product. The yield was 72% based upon the amount ofp-(*p-t-butylphenoxy) phenol charged.

Example XVI Trimethylolanisole triacetate was prepared by reacting 780parts by weight of a 70% aqueous solution (3 moles) of trimethylolphenolwith 136 parts by weight (3.3 moles) of sodium hydroxide in 1430 partsby weight of methanol below 30 C. to form the phenoxide; methylating thephenoxide with 420 parts by weight (3.3 moles) of dimethylsulfate;stirring the methylation mixture for 16 hours at room temperature;adding 60 milliliters of concentrated ammonium hydroxide aqueoussolution; stirring for an additional hour; fiiltering; vacuum-strippingfree of water and methanol; and acetylating with 1329 parts by weight ofpyridine and 1722 parts by weight (16.8 moles) of acetic anhydride at 35C. The reaction mixture was heated to 100 C. for 1 hour; diluted withtoluene; and washed with water, dilute hydrochloric acid and dilutesodium carbonate. The ester product was stripped of volatiles byflashing at 1 mm. Hg absolute and 285 C. to give 472 parts by weight ofproduct. The yield was 48.5%.

Example XVII Dodecylphenyl heptanoate was prepared by dissolving 393parts by weight (1.5 moles) of dodecylphenol and 14.2 parts by weight ofdimethylformamide catalyst in 440 parts by weight of benzene; slowlyadding 421 parts by weight (1.7 moles) of neotridecanoyl chloride;refluxing at 70 to 75 C. for 1 hour; and adding 49 parts by weight ofpyridine. The ester product was washed with dilute hydrochloric acid,dilute sodium hydroxide, and filtered to give 488.5 parts by weight ofproduct.

Example XIX Dixylenyl succinate was prepared by azeotroping 866 parts byweight (7.09 moles) of xylenol with 440 parts by weight of benzene;adding 78.4 parts by weight of dimethylformamide catalyst; slowly adding506.4 (3.27 moles) of succinylchloride at 70 to 80 C. for 1 hour; andadding 147 parts by weight of pyridine at 80 C. The ester product waswashed with water, dilute hydrochloric acid and dilute sodium hydroxide;stripped free of volatiles; flashed at 245 to 247 C. pot temperature and230 to 234 C. vapor temperature at 1 mm. Hg absolute; dehydrated;decolorized with charcoal; and filtered to give 823 parts by weight ofproduct. The yield was 77.5%.

Example XX Dixylenyl azelate was prepared by azeotroping 590 parts byweight (4.8 moles) of xylenol with 440 parts by weight of benzene untildry; slowly adding a solution of 478 parts by weight (2.12 moles) ofazelyl chloride in 220 parts by weight of benzene and 28.4 parts byweight of dimethylformamide catalyst at 90 C.; heating at 120 C. for 2hours; and adding 147 parts by weight of pyridine at 70 C. The reactionproduct was washed with water, dilute hydrochloric acid and dilutecaustic; vacuumflashed at 260 to 270 C. pot temperature and 250 to 260C. vapor temperature at 1 mm. Hg absolute; dehydrated; decolorized withcharcoal; and filtered to give 656 parts by weight of product. The yieldwas 78%.

Example XXI Dixylenyl sebacate was prepared by azeotroping 562 parts byweight (4.61 moles) of xylenol with 440 parts by weight of benzene untildry; adding 19 parts by weight of dimethyl formamide catalyst; slowlyadding 500 parts by weight (2.09 moles) of sebacyl chloride at 70 to 80C.; heating to 120 C. for 1 hour; adding 98 parts by weight of pyridine;and heating to 70 C. for 2 hours. The ester product was washed withwater, dilute hydrochloric acid and dilute sodium hydroxide; strippedfree of volatiles; flashed at 280 to 285 C. pot temperature and 264 to267 C. vapor temperature at 1 mm. Hg absolute; dehydrated; decolorizedwith charcoal; and filtered to give 692 parts by weight of product. Theyield was 80.8%.

Example XXII Trimethylolanisole tribenzoate was prepared by saponifying123 parts by weight (0.38 mole) of trimethylolanisole triacetate with 52parts by weight (1.3 moles) of sodium hydroxide in 550 parts by weightof methanol by refluxing for 9 hours; neutralizing the product withglacial acetic acid; vacuum-stripping and adding dioxane until themethanol was removed; chilling to provide trimethylanisole; and adding490 parts by weight of dry pyridine and 168 parts by weight (1.2 moles)of benzoyl chloride. The reaction product was washed with water, dilutehydrochloric acid and dilute sodium carbonate; decolorized withcharcoal; and filtered to give 173 parts by weight of product.

Example XXIII p-(p-t-Octylphenoxy)phenol, 191 parts by weight (0.64mole), one liter of toluene, and three ml. of dimethylformamide werecharged to a two-liter, three-neck flask, and the mixture was heated to80 C. Neoheptanoyl chloride, 105 parts by weight (0.74 mole), was placedin a dropping funnel and added slowly to the reactor. After completeaddition of the acid chloride, the mixture was stirred at 88 C. for onehour, then cooled to 25 C. and 80 ml. of pyridine was added. Thesolution was heated to C., stirred at this temperature for three hours,then allowed to stand overnight. It was washed with one liter of water,twice with dilute hydrochloric acid, three times with 20% sodiumhydroxide and finally with water. The solvent was stripped off undervacuum, then the product was distilled to give 127 parts by weight(48.5% yield) of a clear oil boiling over a range of 187- 192 C. at 0.1mm. HgA.

Example XXIV m-(p-t-Octylphenoxy)phenol, 125 parts by weight (0.42mole), and one pint of toluene were placed in a one-liter, three-neckflask fitted with reflux condenser and dropping funnel. Pyridine, 80ml., was added to the solution and neoheptanoyl chloride, 62 parts byweight (0.42 mole), was added dropwise. This mixture was stirred for onehour at 30 C. following the complete addition of the acid chloride, andthen allowed to stand overnight. The product was heated to C. for twohours, cooled to 30 C. and then washed with water and dilutehydrochloric acid. It was then stripped of solvent and vacuum distilled.The boiling point was 182 196 C. at 0.5 mm. HgA, with a yield of 88parts by weight (51%).

Example XXV p-(m-Phenoxyphenoxy)phenol, 153 parts by weight (0.55 mole),450 parts by Weight of toluene and three ml.

of dimethylformamide were placed in a one-liter, threeneck flask. Waterwas removed by azeotropic distillation. The addition of neoheptanoylchloride, 90 parts by weight (0.61 mole), was begun at 70 C.Approximately 30 parts by weight was added at this temperature and whenno reaction was observed, the temperature was gradually increased untilthe reaction began (90 C.). The remainder of the acid chloride was addedslowly at this temperature. The mixture was stirred for 45 minutes,cooled to 40 C. and 50 ml. of pyridine was added. The solution wasallowed to stand overnight, heated with stirring at 70 C. for one hour,then washed twice with dilute hydrochloric acid, four times with dilutesodium hydroxide, and finally with water to neutrality. Flashdistillation gave 134 parts by weight (62% yield) of a mobile oil, B.P.212 C. at 0.5 mm. HgA.

Example XXVI 3,4'-dihydroxydiphenyl ether, 76 parts by weight (0.38mole), three ml. of dimethylformamide, and 500 ml. of toluene wereplaced in the reactor and heated to 80 C. Neoheptanoyl chloride, 125parts by weight (0.84 mole), was added slowly over a period of 30minutes with the temperature kept at 80-90 C. When the evolution ofhydrogen chloride gas ceased, the solution was cooled to 30 C. and 80ml. of pyridine was added slowly. The mixture was then stirred at 90 C.for one hour, then washed with dilute hydrochloric acid and water.Distillation gave 137 parts by weight (73% yield) of a light yellow,mobile oil having a boiling range of 188-195 C. at 0.1 mm. HgA.

Example XXVII 4,4'-dihydroxydiphenyl ether, 100 parts by weight (0.5mole), was placed together with 500 ml. of toluene and three ml. ofdimethylformamide in a one-liter, three-neck flask fitted with stirrer,modified Dean-Stark trap, reflux condenser, dropping funnel, andhydrogen chloride gas trap. Residual water was removed by azeotropicdistillation. Neoheptanoyl chloride, 162 parts by weight (1.09 moles),was placed in the dropping funnel and added slowly to the reactor at85-90 C. When all the neoheptanoyl chloride had been added and evolutionof hydrogen chloride gas had ceased, the product was cooled to roomtemperature and 80 ml. of pyridine was added. The mixture was heated to80-90 C. for three hours, then allowed to stand overnight.

The product was washed with dilute hydrochloric acid, 20% sodiumhydroxide, and finally with water, stripped of solvent under vacuum, andtreated with decolorizing carbon. Vacuum flash distillation gave 136parts by weight (64% yield) of colorless material, B.P. 199-202 C. at0.1 mm. HgA.

Example XXVIH Resorcinol, 24 parts by weight (0.22 mole). 100 ml. ofbenzene, and two ml. of dimethylformamide were placed in a 500 ml.,three-neck, round-bottom flask equipped with a dropping funnel, stirrerand hydrogen chloride gas trap. This solution was heated to 70 C. andcrude neooctanoyl chloride was added slowly at 7 80 C. When theevolution of hydrogen chloride gas ceased, the mixture was cooled, 20ml. of pyridine was added and the solution was allowed to standovernight. This product was then washed with water, dilute hydrochloricacid, and dilute sodium hydroxide and the solvent was removed in vacuo.Distillation of the resulting oil gave 52 parts by weight (60% yield) ofproduct boiling in the range 155172 C. at 0.3 mm. HgA.

Example XXIX Resorcinol, 34 parts by weight (0.31 mole), three ml. ofdimethylformamide, and 350 parts by weight of toluene were charged tothe reactor flask and heated to 75 C. 2,2,4,4-tetramethylphentanoylchloride, 115 parts by weight (0.65 mole), was then added slowly from adrophad ceased, the product was stirred for an additional two hours at95 C., then cooled to 25 C. and ml. of pyridine was added. The solutionwas then heated to 100 110 C. and stirred at this temperature forminutes, and allowed to stand overnight. The product was washed twicewith one liter of dilute hydrochloric acid, three times with one literof 20% sodium hydroxide, and finally with water until neutral. Flashdistillation gave 45 parts by weight (37.2% yield) of product, boilingin the range of 153-163 C. at 0.15 mm. HgA.

Example XXX Resorcinol, 330 parts by weight (3 moles), two liters oftoluene and five ml. of dimethylformamide were placed in a five-liter,three-neck flask and heated with stirring to 75 C.2-methyl-2-ethy1hexanoyl chloride, 1165 parts by Weight, (6.6 moles),was added slowly from a dropping funnel. The temperature was maintainedat 7585 C. during the addition of the acid chloride. After refluxing themixture for two hours, it was cooled to 65 C. and ml. of pyridine wasadded. The solution was stirred for six hours and then washed withdilute hydrochloric acid, dilute sodium hydroxide, and finally withwater. Solvent was stripped under vacuum and the ester was distilled.Boiling point ranged from 188204 C.; the wide range was due todifliculty experienced in maintaining a uniform pressure. The pressurevaried from 0.12.0 mm. HgA. A yield of 1050 parts by weight (78% oftheory) of a water white oil was obtained.

Example XXXI p-t-Butylphenol, 475 parts by weight (3.17 moles), 500 ml.of toluene, and three ml. of dimethylformamide were placed in atwo-liter, three-neck flask and water was removed from the phenol byazeotropic distillation.

Adipoyl chloride, 264 parts by weight (1.44 moles), was added slowly tothe reactor at 70-75 C. Following complete addition of the acidchloride, the reaction mixture was stirred at 75 C. for one hour, thencooled to 50 C. and 100 ml. of pyridine was added. After stirring thesolution for two hours, it was washed twice with dilute hydrochloricacid, twice in hot (60 C.) dilute sodium hydroxide, and twice with hotwater. The ester was allowed to crystallize overnight, vacuum filtered,then recrystallized once from heptane to give 330 parts by Weight (59%yield) of a white crystalline solid.

Example XXXII p-t-Butyl'phenol, 384 parts by weight (2.56 moles), 600ml. of toluene, and three ml. of dimethylformamide were charged to thereactor flask and heated with stirring to 70 C. Azelaoyl chloride, 250parts by weight (1.11 moles), was added cautiously from a droppingfunnel. The reaction was vigorous and instantaneous. After completeaddition of the acid chloride, the mixture was stirred at 70 C. for twohours, then cooled to 55 C. and 100 ml. of pyridine was added. Afterstirring the solution for one hour, it was washed twice with dilutehydrochloric acid, three times with dilute sodium hydroxide, and twicewith water, then allowed to crystallize. It was then vacuum filtered anddried to give 320 parts by weight (62% yield) of crude product.

Example XXXIII p-t-Butylphenol, 276 parts by weight (1.84 moles), 600parts by weight of toluene, and three ml. of dimethylformamide wereplaced in a two-liter, three-neck flask and heated with stirring.Sebacoyl chloride, 200 parts by weight (0.84 mole), was added slowlyfrom a dropping funnel when the reactor temperature reached 60 C. Atemperature of 60--65 C. was maintained during the time of addition (25minutes). The solution was stirred Example XXXIV m-t-Butylphenol, 475parts by weight (3.17 moles), and 600 parts by weight of toluene wereplaced in a twoliter, three-neck flask fitted with stirrer, condenser,hydrogen chloride gas trap, and Dean-Stark trap. Water was removed byazeotropic distillation. The mixture was then cooled to 75 C., three ml.of dimethylformamide was added and the addition of adipoyl chloride, 264parts by weight (1.44 moles), was begun. The acid chloride was ExampleXXXVI Nonylphenol, 215 parts by weight (0.98 mole), was placed in atwo-liter flask with 600 ml. of toluene and three ml. ofdimethylformamide. Adipoyl chloride, 82 parts by weight (0.45 mole), wasadded slowly to the flask at 65-70 C. The solution was heated Withstirring to 70-80 C. for three hours, then cooled to 55 C. and 100 ml.of pyridine was added. The mixture was allowed to stand overnight. Thecrude product was washed twice with dilute hydrochloric acid, five timeswith hot, dilute sodium hydroxide and twice with water. Solvent Wasflashed in vacuo, and the product was treated with decolorizing carbon.Vacuum filtration gave 200 parts by Weight (83% of theory) of a viscousyellow liquid.

The term parts by weight refers to grams.

Table I, below, is a listing of the physical properties of somerepresentative esters synthesized according to this invention.

TABLE I Pour Acid No. Viscosity Wt. M.P. point (mg at 450 F. percentEster 0.) F.) KoH/gm) (cs.) OH

Resorcinal dilieptanoate 1. 5 0. 6 0. 76 0. 4 Hydroquinone diheptanoate.56. 6- 0. 1 0.87 0. 6 Bispheuol A diheptanoate -32 4 0.6 1. 40 0. 1Resoreinol dineoheptanoate 55 0. 1 1. 73 0. 1 Bisphenol Adineoheptanoate. 10 0. 1 1. 7 0. 5 Resoreinal dineodeeanoate 0 0. 2 1. 00. 2 Resorcinol diueotridccanoate 1 0. 1 1.3 0. 1 Resoreinal dipivalate765-77. 8 0. 0 0. 71 Bisphenol A dibenzoate l61. 0-162. 3 0. 1 2. 7 0. 1Hydroquinone dibenzoate. 205-208 0.4 1. 3 0. 1 3,4 bisphenol ether(lineuheptanoate 10 0. 1 l. 2 0. 77 Resoreinal dibenzoate 116.8-117A 0.3 1. 2 0. 6 1-(p-t-butylphenoxy)pheuyl neoheptanoate 3 0. 1. 02 0.I\I-(p-octylphenoxy)pheny1 neoheptanoate 28 0. 1 1. 2 N.'1P-(p-t-pentylphenoxy)phenyl neoheptauoa -3. 5 N.T. 1. 06 N .T1-(p-t-pentylphenoxy)pheuyl neopentanoate 23 N.T. 1. 0 N .TP-(m-t-butyl-phenoxy) phenyl neoheptanoate 1 N.T. 0. 94 N.T.P-(ni-t-butyl-phenoxy) phenyl neopentanoate. 82. 5-92. 5 N.T. 0.82 N.

N.T.:Not tested.

added to the reactor dropwise over a period of 30 min utes with thetemperature kept at 75 to 80 C. The mixture was stirred at 77 to 80 C.for one hour then cooled to C. and 80 ml. of pyridine was addedcautiously. The solution was then stirred for one hour, washed twicewith dilute hydrochloric acid, four times with dilute sodium hydroxideand finally with water until neutral to litmus. Approximately 400 ml. ofsolvent was flashed 011 under vacuum, and the product was allowed tocrystallize overnight. The product, after dehydration, consisted offluffy white crystals; 450 parts by weight was obtained, a yield of 76%.

Example XXXV di-t-Pentylphenol, 515 parts by weight (2.2 moles), 500parts by weight of toluene, and three ml. of dimethylformamide wereadded to a two-liter, three-neck flask. The mixture was heated withstirring to C. and adipoyl chloride, 183 parts by weight (one mole), wasadded dropwise over a period of one hour. The mixture was heated withstirring to C. for two hours, then cooled to 60 C. and ml. of pyridinewas added to catalyze completion of the reaction. The crude product wasWashed twice with dilute hydrochloric acid, five times with hot (60 C.),dilute sodium hydroxide and finally with water to neutrality. Solventwas stripped under vacuum; the product was treated with decolorizingcarbon and then vacuum filtered to give 518 parts by weight (80% yield)of a viscous, yellow oil.

Gas turbine engines are a most important source of power today.Turboprop and turbojet engines are in service with both the military andcommercial aviation interests and gas turbine engines are starting tobecome commercial power for boats and cars. As is well known, a turbineconsists of a shaft having blades or buckets spaced therearound. Ahigh-temperature fluid under high pressure is directed against theblades or buckets usually parallel to the axis of the shaft, and theenergy of the fluid is transferred to the turbine thus causing the shaftto rotate and permitting it to do work. Gas turbines operate elfectivelyat about 500 to 1000 C. with bearing temperatures preferably about 525F. to 600 F. Lubricants for such turbines are subjected, in use, totemperatures in this range.

Turbine engines are lubricated from a central lubricant supply. Thelubricant is fogged into the bearing chamber, in a so-called mistapplication, to lubricate the ball or roller bearings of the turbine.The lubricant also performs the important function of cooling thegraphite seals between the turbine blades and the combustion chamber.After lubricating the roller or ball bearings, the lubricant iscollected in sumps from which it is pumped back to the lubricant supply.The lubricant is degassed before being recirculated by centrifuging toremove any gas or volatiles (cracked lubricant molecules primarily)which have been introduced to the system. This same lubricant is alsoused to lubricate the drive gears for auxiliary power chains driven bythe turbine. In the case of jet engines, these auxiliary drive chainscan operate a compressor, air-conditioning units, guidance systems,

it to a dry air flow of 1.2 liters per hour for 6 hours at varioustemperatures (347 F. and 450 F.) after which time the esters were testedto determine their physical properties. Table III below is a compilationof 5 data taken from these tests.

Ester l3 weapons systems, and the like. The lubricant is operable in themesh of the gears and therefore must withstand extremely high pressures.It is also very important that the lubricant must be temperature andoxidative stable in order to withstand the conditions encountered inturbine lubrication applications.

1 17 986723 9 tg JTELJ L2 L2 LL m .m .m NN o .mt d M d 1 P um t w re? mN N NN N N mo m w M 1 274000595 11 297.333 0 Eu w F LmL L LaaL 0N.N.00000000 1 m \J m0 0 Q 1 l S ym t 521 3 23 o motor. orator. T m m e m mwwF Ethernet.. N N NN N N M m omw W N NNNN N Wm m a 1 t w e m m w 7 64609799 8 d v.6 H M i. m 99 4361 813 tmm o 0 113 7 0 wmb mmdu o m wMMELMLLEZLLE NN a wm .wwwww mm N N N a m T a en r T n m s.m lmlll aensissesean 0 .08 U V n t a a O O O o 04 100000101 N N NN N W fiwm tmmmm m m shwmrmrrm H 7 1 TI m wmwww m 606 281 1 Imme 1w; mvm m mm m Fmairmmmmoaom m m I Iwm mfi e R R m .0 N N N O a I c I I O nmmmmm nmmmmmmm RmmW12345 m. 7 e0 03 I MHWMWM u wm ma cmu m S m 16 43 512 m pmo wdmm s N F ar aaa moarm .ww mwm @mmw m m M m m m. N N N .mm m m "ww wm 9 Hdd d unn d mu o ny mmr ra I m mildl uflfll mi .MN e Ob.l H 0 SM. I645314012059 uo 0 o uhm FT= V. F 5 ..1fi.. qmmm mm w as M ad W d E Q L450262 mn mm w m mm we n.. p... m .0. mwv..m%.mn%%.wmyu.m izN x 6 m A 7RRHBRB RRBRHa e t c m T a m wn F N F 57 5445 numcfl fihm m W N NNNN N .1dm m m m 7 n n W N w ad 30 0427 649 W a t eR W F 0.2T1OQ5T923T .m amm.ma H N N N e m ak e m u mn m" mrc W "e O .1E.EC.J 2m t 10 1.. b .me .0 mu b .n g 0 .a n s 7 ir n u "mu "w 6(fi w ea. .u m f ses .a G O m sele 0tn te C ohet t mn a m r. r. 3 n o t mt 0.m afi smn 6 on m lwm em m m mmmmfi a I 1D. O Z h 0 er 8 m m mmo do n ae ga w h e eemfl 6 H p d d d .1.ln 1 li. 1H0 m umm m m m mm mmm r g Pr. flfl o oomomh ow 0 nn n nn n 0.m m mm m r mdmmmmm n m d mo m r mm m mm mm E an hlk w ss s ssws 03.11 aaS eevrmem i ta Pam9 ct E RRHBRBRRBRHQW 1 At F. N.T.=Not tested.

The oxidation stability test is conducted by placing 6. Resorcinoldi-(2,2,4,4-tetramethylpentanoate). 25 grams of the ester under test ina tube and subjecting 7. Resorcinol di-(2-methyl-2-ethylhexanoate).

References Cited UNITED STATES PATENTS 3,341,574 9/1967 Taylor et al.260485 3,205,270 9/1965 Jaruzelski et al. 260613 2,345,006 3/1944 Rosset al. 260-4l0.5

FOREIGN PATENTS 1,175,829 4/ 1959 France.

OTHER REFERENCES Ingle et al.: J. Indian Chem. Soc. vol. 26, pp. 56974(1949) QB 1.15j.

Cruickshank et al. J. Chem. Soc. (1938) 2064-71. \Aelony: J. Amer. OilChemists Soc. vol. 32, (1955), pp. -71.

LORRAINE A. WEINBERGER, Primary Examiner R. S. WEISSBERG, AssistantExaminer US. Cl. X.R. 260476, 479, 613

